Cleaning composition



Patented Sept. 4, 1951 GLEAN ING COMPOSITION Ernest R. Irwin, Whiting, Ind., assignor to Standard Oil Company, Chicago, Ill., a corporation of Indiana No Drawing. Application December 26, 1947,

Serial No. 794,125 '1 l i 2 Claims.

H 1 i This invention relates to cleaning composition and more particularly to compositions suitable for cleaning machinery and machine parts of oil, grease, sludge and varnish-like deposits resulting from the decomposition of lubricants of such machines.

An object of the present invention is to provide an improved composition for cleaning paint, oil, grease, sludge and the like, from machine parts. Another object of the invention is to provide a composition for removing from parts of internal combustion engines, sludge, carbonaceous material, and varnish-like deposits resulting from the oxidative decomposition of the lubricant of such engines. Another object of the invention is to provide a compositon which will remove oil, grease and products resulting from the oxidation of lubricating oil from engine parts and which will brighten the dull surfaces of metal parts after the removal of said oil, sludge, etc. Other objects and advantages will become apparent from the following description of my invention.

The composition of the present invention consists essentially of a combination of alkali sulfon'ates, aromatic hydrocarbons boiling above about Sulfonates Aromatic hydrocarbons (boiling point above 400 F.) 10- 50 Chlorinated hydrocarbonsn 10-50 Organic acid 1.0-l0 Cresylic acid 0-20 C2-C5 aliphatic alcohols. 0-10 Amine 0-2 Water 0-10 The sulfonates in the above formulation consist of detergent type and/or emulsifying-type sulfonates. This type of sulfonate is characterized by being soluble in-both oil and water.

The detergent componentof the composition canbe any preferentially water-soluble detergent and preferably the preferentially water-soluble petroleum sulfonates obtained. in thetreatment Percent 1 2 of petroleum oils with a sulfonating agent, such as concentrated sulfuric acid or fuming sulfuric acid. Other suitable detergents are the alkali metal alkylated aromatic sulfonates having from about 10 to about 16 carbon atoms in the alkyl group, such as for example, the alkylated aromatic sulfonates described in Kyrides Patents 2,161,174 and. 2,232,118 orFlett Patents 2,283,119 and 2,249,757. r i

The petroleum sulfonates are those obtained in the treatment of petroleum oils to obtain highly refined products of the type of transformer oils, turbine oils, distillate oils, etc., in which the petroleum oils are treated successively with a number of portions of concentrated sulfuric acid, (i. e., aboveabout 95% strength), or fuming sul-j furic acid. The sulfuric acid is usually added in dumps of about /2 poundper gallon of oil, the total quantity of acid treated depending upon the oil being treated and the desired final product.

Usually from about ,3 pounds to, about 9 pounds of sulfuric acid per gallon of oil is used. Some of the sulfonic acids resulting from the treatment of the oil with the sulfuric acid are preferentially oilsoluble, a major proportion of which remain in the oil layer after the removal of the acid sludge resulting from the acid treatment of the oil. These can be removedfrom the oil by neutralizing the acid -treated oil with. an alkaline agent such as ammonia, or an alkalimetal hydroxide, preferably sodium hydroxidato form the corresponding sulfonic acid soaps which are then extracted from the oil with to 80% aqueous alcohol solutions or other suitable means. Because of their characteristic mahogany color these sulfonates are known in the petroleum art as mahogany soaps. While most of the preferentially oil-soluble sulfonates areobtained from the acid-treated oil, they can be recovered from the acid sludge by suitablesolvents as preferentially oil-soluble sul fonic acids. As produced commercially the sulfonates contain approximately 50% to unsulfonated hydrocarbon oil and other common impurities such as water, sodium sulfate and free caustic. The formulas given to illustrate my in-, vention refer to the commercial sulfonate product. Hence the pure alkali metal sulfonate con-, tent will be from about 33% to about 50% of the amountshown in the specification and claims.

The preferentially oil-soluble sulfonic acids have molecular weights. in the range of from about 350 to about 525 and they vary with their molecular weight from very oil-soluble products. to products which are'substantially oil-insoluble; and preferentially water-soluble. Mahogany acids, namely those obtained by treating a petroleum distillate having a viscosity within the range of about 55 to 60 seconds Saybolt Universal at 100 F., with about four pounds of fumin sulfuric acid have molecular weights of about 400 to 410, and are the least oil-soluble of the so-called mahogany acids, and the mahogany acids having molecular weights of about 470-525 are the most oil-soluble and least water-soluble sulfonic acids. The alkali metal soap, preferably sodium soap of 1 these low molecular weight mahogany acids, namely, those having molecular weights of about 400 to 410, are particularly wellsuited 'foruse in the present invention.

The alkali metal soaps of petroleum sulfonic acids having molecular weights above 425-450 can be used in the present invention, but ip'referably in combination with a preferentially water-soluble soap or detergent. For example, the sodium soap of a mahogany acid having molecular weights of about450- l'70 can be used in combination with a sodium rosin soap, an alkylated aromatic 'sul-fonate of 12 to 16 carbon atoms, or a preferentially water-soluble petroleum sulfonate.

In the formulation of the present invention I find it advantageous to use in combination with the alkali metal soap of mahogany acids of 400 410 molecular weights, an alkali metal soap, e. g. sodium soap of mahogany acids of 470-525 molecul'ar weight, which are extremely oil-soluble and water-insoluble.

In addition 'to'th'e mahogany soaps which are usually recovered from the acid-treated'oil, there isanother class of sulfonic acids -recoverable from the acid sludge resulting from the treatment of petroleum oils'withsulfuric'acid. The acid sludge sul'fonic acids, which are generally referred to as green acids because of their characteristic greenish color, are preferably preferentially water-soluble and have .molecularweights of from about 430 to about 450. The green .acids are mixtures of very water-soluble sulfonic acids known as black acids, intermediatewater-soluble sulfonic acids which. are referred to as detergenttyipe sulfonic acids and preferentially oil-soluble sulfonlc acids which are deep red'to brown in color and are usually referred toas brown acids. The brown acids which are preferentially oilsoluble are less oil-soluble than the mahogany acids. The green acids can be recovered from the acid sludge by adding water to. the sludge to dilute the sulfuric acid to a concentration of 20 to 30 percent at which concentration the green acids separate to form a supernatant layer. Alternatively,- the green acids can be extracted from the sludge by using water-soluble solvents or mixtures of organic solvents with water. The detergent-type preferentially water-soluble acid sludge canbe recovered as such from the acid sludge by eXtraction with benzene or carbon tetrachloride or mixtures thereof. The present invention contemplates employing'alkali metal brown acid soap'in place of the soaps of low molecular weight mahogany acids, or'mixtures of the preferential water-soluble 'sulfonates with the preferential oil-soluble sulfonates.

The aromatic hydrocarbons employed in the herein-described composition are mixtures of aromatic hydrocarbons produced by the'catalytic conversion of aliphatic hydrocarbons by the socalled hydroforming, process. This mixture is known in the petroleum refining art at catalytic reformed naphtha bottoms, hydroformer polymer or bottoms. A process by which the hydroformer 4 polymer can be obtained is described in U. S. P. 2,320,147. Briefly, the process comprises treating a virgin or cracked naphtha or a mixture thereof with a solid porous hydroforming catalyst, such as an oxide of a metal of groups 2 to 6 of the periodic system, and particularly an oxide of a group 6 metal, such as chromium or molybdenum suitably supported on alumina or magnesia. The conversion is suitably carried out at a temperature of from about 850 F. to about 1050 F., and if desired, in the presence of hydrogen. The hydroformer reaction products are fractionated by taking overhead a catalytically reformed gasoline of suitable end point, and recovering a higher boiling material a'sbottoms which boil from about 400 F. toabout 750 F., and have gravities of a from about API to about 13 API. The bottoms referred to herein and in the appended claims as hydroformer polymer is a complex mixture of monoand polycyclic aromatics. A typical vacuum distillation of a hydroformer sample having a gravity-of about 12 lowing:

Fraction Component Dimethylnaphthalene's.

Methyldiphenyls Trimethylnaphthalenes.

Fluorene.

Anthracenes and Phenanthrena threnes. Pyrene.

Tetracyclics and higher;

A representative hydroformer bottoms fraction exhibits the following physical properties:

API gravity 11- 22 Refractive index n 1.59111 Specific dispersion? 264' ASTM distillation initial 448 F."

Max. (-92% off) 750 F.

While the entire hydroformer polymer can -be" The organic acid can-bean-y high molecular weight organic acid, such as for example, oleic acid, stearic acid, palmitic acid, naphthenic acid, etc., althoughI prefer to use naph'thenic acid. The "nap'ht'henic acids consist of the acids recoverable from the alkali washing of naphthenic base crude oil fractions andha've molecular weights ranglngfrom' about 200 to about 300. Like the mahogany acids 'referre'dto above, the alkali naphthenates are soluble'in both oil and Water.

API shows the-fol Methyl'anthracen'es and l\lethylphenan- Volume Per Cent Range Preferred Sodium soap of mahogany acid (400-410 molecular weight) 15 to 28 20 Sodium soap of mahogany acid (470500 molecular weight) l 2 to '7 5 Hydroformer bottoms (400 F.600 F.

boiling range) 12 to 20 i Monochl0rbenzene 25 to 35 30 Oresylic acid... 10 to 20 i4 Isopropyl alcohol. 3 to 7 5 Naphthenic acid. 3 to 6 Water 3 to 6 4 Plus Monoethanolamine 0. 25 to 1.0 0 5 The organic acid, such as naphthenic acid, used in the formulation of the present invention should be in excess of from about 1% to about 4%.

Dirty engine parts are readily cleaned of oil, grease, sludge, etc., by immersing them, preferably at about 80-150 F. in the cleaning composition of the present invention for a time sufficient to permit the solution to dissolve and/or remove the oil, sludge, etc., and then removing the clean parts from the cleaning solution. After removing the cleaned parts from the cleaning solution they are preferably rinsed in water or a hydrocarbon solvent, such as kerosene or the like. Metal parts so treated come out of the'cleaning solution clean and bright. The organic acid, e. g., naphthenic acid and the amine, e. g., monoethanolamine, adjust the corrosion and brightening effects on iron, copper and zinc alloy to a condition in which corrosion is very slight but sufficient to brighten the dull surfaces.

While I have described my invention by reference to specific and preferred embodiments thereof the same are given by way of illustration only and are not intended as defining the limitations of the invention except insofar as the same is defined by the following claims:

I claim:

1. A cleaning composition consisting essentially of the following materials in the approximate proportions by volume:

Percent Alkali metal soap of mahogany sulfonic acids having molecular weights of l00-l10 to 28 Alkali metal soap of mahogany acids of 470 to 500 molecular weight--- 2 to 7 Catalytic reformed naphtha bottoms having initial boiling point above about 400 F. and final boiling point below about 600 F 12 to Monochlorbenzene to 35 Cresylic acid 10 to 20 Isopropyl alcohol 3 to 7 Naphthenic acid 3 to 10 Water 3 to 6 Monoethanolamine 0.25 to 1.0

2. A composition for cleaning surfaces consisting essentially of about 20% by volume, of sodium soap of a mahogany sulfonic acid, having molecular weights of about 400 to 410, about 5% by volume of sodium soap of mahogany acids having molecular weights of about 470 to about 500, about 10% by volume of catalytic reformed naphtha bottoms having a distillation range of from about 400 to about 600 R, about by volume monochlorbenzene, about 14% by volume cresylic acid, about 5% by volume, isopropyl 1 alcohol, about 6% by volume, naphthenic acid about 4% Water, and about 0.5% by volume monoethanolamine, said finished product having from about 1% to about 4% excess acidity.

ERNEST R. IRWIN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS 

1. A CLEANING COMPOSITING ESSENTIALLY OF THE FOLLOWING MATERIALS IN THE APPROXIMATE PROPORTIONS BY VOLUME: 